Photochromic benzopyran compounds

ABSTRACT

Benzopyran compounds represented by the formulas: ##STR1## wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10  are selected from hydrogen, a stable organic radical, a heterocyclic group, halogen, a nitrogen-substituted group, and a nitrogen-substituted ring compound.

This is a continuation of application Ser. No. 08/478,263, filed Jun. 7,1995.

BACKGROUND OF THE INVENTION

The present invention generally relates to benzopyran compositions andto benzopyran compounds. More specifically, the present inventionrelates to photochromic benzopyran compounds and to photochromicbenzopyran compositions.

Photochromism generally concerns the ability of a compound to reversiblychange color under different light conditions. One particular type ofphotochromic phenomenon concerns the reversible change in color of acompound from an original color to a different color when the compoundis exposed to a source of ultraviolet radiation, such as solar radiationor light radiated from a mercury or xenon lamp. The photochromiccompound fades to the original color within a period of time after thecompound is isolated from the ultraviolet radiation, such as by placingthe compound in a dark room.

Various products, including optical lenses, incorporate the principal ofphotochromism. For example, photochromic compounds, such asnaphthopyrans, are incorporated into plastic ophthalmic lenses to effectcolor changes in the plastic lenses when the lenses are exposed toparticular lighting conditions. Additionally, different photochromiccompounds may be blended to create a color effect that is different fromthe respective color effects of the individual photochromic compounds.As an example, a first photochromic compound that turns orange or redwhen activated by light and a second photochromic compound that turnsblue when activated by light may be blended to form a photochromicmixture that produces a shade of gray when activated by light

Several types of photochromic compounds have been reported which exhibitchanges in color when exposed to ultraviolet light. One particular classof photochromic compounds includes the 3,3-disubstituted naphthopyrans.One specific group of 3,3-disubstituted naphthopyrans includes the3H-naplitho 2,1b!pyrans. The color response of the 3H-naphtho2,1b!pyrans to ultraviolet light extends to purple, red, orange oryellow, depending upon the composition and structure of the particular3H-naphtho 2,1b!pyran. A general expression of the 3H-naphtho2,1b!pyrans is provided in graphical formula I: ##STR2## where R₁ and R₂are substituents attached to the pyran ring at the position indicated.

Several photochromic compounds are described in U.S. Pat. No. 3,567,605to Becker. The Becker patent describes chromenes and chromenederivatives which are photochromic at relatively low temperatures, Thepatent also describes chromenes and chromene derivatives which arephotochromic at room temperature, such as diphenyl-3H-naphtho2,1b!pyran, where R₁ and R₂ of formula I are each unsubstituted phenylgroups.

Additional photochromic compounds are described in U.S. Pat. No.4,931,221 to Heller et al. One type of photochromic compound describedin Heller generally has the form of graphical formula I with R₁ and R₂being cyclopropyl radicals and with any of various substituents includedon the naphtho portion of the naphthopyran rings. Heller reports alarger bathochromic shift in the visible spectrum of 3H-naphtho2,1b!pyrans that include the cyclopropyl radicals, as compared to3H-naphtho 2,1b!pyrans that include alkyl groups or a spirocycloalkylgroup in place of the cyclopropyl radicals.

Other photochromic compounds are described in U.S. Pat. No. 5,066,818 toGemert et al. One photochromic compound class described in Gemertgenerally meets graphical formula I with one of R₁ and R₂ being asubstituted phenyl radical, with one of R₁ and R₂ being either asubstituted or unsubstituted phenyl radical, and with varioussubstituents included on the naphtho portion of the naphthopyran rings.Gemert lists various non-aryl groups as potential substituents of thephenyl radicals of R₁ and R₂. Gemert reports a range of decolorizationrates associated with the 3H-naphtho 2,1b!pyrans that include the phenylradicals as R₁ and R₂.

Additional photochromic compounds are described in U.S. Pat. No.5,106,998 to Tanaka et al. Tanaka describes compounds in which R₁ and R₂of graphical formula I are alkyl groups. Tanaka reports several fadetimes and maximum absorption wavelengths associated with various3H-naphtho 2,1b!pyrans that include the alkyl radicals as R₁ and R₂ informula I.

U.S. Pat. 5,238,981 to Knowles teaches a 3H-naphtho 2,1b!pyran compoundin which R₁ and R₂ of graphical formula I are each selected from a groupof organic radicals that includes phenyl and naphthyl. The organicradicals placed at R₁ and R₂ are either substituted or unsubstituted.Potential substituents of substituted organic radicals placed at R₁ andR₂, provided that one of the organic radicals placed at R₁ and R₂ is aphenyl group, include various non-aryl groups. Various potentialsubstitutions on the naphtho portion of the naphthopyran ring aretaught, including an 8-methoxy substitution. Knowles states that thenumber eight carbon atom substitutions, such as the 8-methoxysubstitution, cause a bathochromic shift in the visible spectrumassociated with activated forms of the 3H-naphtho 2,1b!pyrans and in theultraviolet spectrum of unactivated forms of the 3H-naphtho 2,1b!pyrans.

Additional photochromic compounds are described in U.S. Pat. No.5,244,602 to Van Gemert. Van Gemert describes 3H-naphtho 2,1b!pyrans inwhich R₁ and R₂ of graphical formula I are each phenyl, naphthyl,various heterocyclic groups, and certain non-aryl groups. Van Gemertalso discusses substitution of various non-aryl substituents into anyphenyl, naphthyl, heterocyclic, and non-aryl groups placed at R₁ and R₂.Van Gemert also states that certain substitutions at the number 5 carbonon the naphtho ring causes a bathochromic shift of the absorptionmaximum of the 3H-naphtho 2,1b!pyrans.

U.S. Pat. No. 5,274,132 to Van Gemert describes certain 3H-naphtho2,1b!pyrans in which R₁ of graphical formula I is a phenyl group, anaphthyl group, a furyl group, or a thienyl group and in which R₂ ofgraphical formula I is an arylalkenyl radical. Van Gemert describes abathochromic shift associated with the 3H-naphtho 2,1b!pyrans thatinclude the arylalkenyl radical, relative to certain other naphthopyransdisclosed in U.S. Pat. No. 3,567,605.

SUMMARY OF THE INVENTION

The present invention includes benzopyran compounds represented by theformulas: ##STR3## wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, and R₁₀are selected from hydrogen, a stable organic radical, a heterocyclicgroup, halogen, a nitrogen-substituted group, and a nitrogen-substitutedring compound. The present invention further includes a photochromicproduct that includes the benzopyran compound and at least onestructural isomer of the photochromic compound.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Novel photochromic compounds have been discovered which enable highwavelength activation and deep coloring. On activation, the novelphotochromic compounds produce colors that are capable of being blendedwith blue-producing photochromnic compounds to form photochromic blendsthat produce remarkably pleasing gray colors when the blends areactivated by ultraviolet radiation. Furthermore, the novel photochromiccompounds have acceptable fade rates and may therefore be desirablyincorporated into a variety of photochromic articles.

Novel benzopyran compounds of the present invention may be representedby graphic formulas IIa and IIb as follows: ##STR4## The method setforth later in this application for producing the photochromicbenzopyran compounds of graphic formulas IIa and IIb forms aphotochromic reaction product that includes two benzopyran compounds,namely, a structural isomer that meets graphic formula IIa and anotherstructural isomer meeting graphic formula IIb,

A variety of substituents may be placed on the pyran portion and thenaphtho portion of the benzopyran rings. For example, the positionsrepresented in graphic formulas IIa and IIb by R₆ ', R₇ ', R₈ ', and R₉' may each be filled with hydrogen; a stable organic radical, such asalkyl, alkoxy, unsubstituted or substituted phenyl, unsubstituted orsubstituted phenoxy. naphthyl naphthoxy, cycloalkyl, furyl, alkoyl,alkoyloxy, aroyl, or aroyloxy; a heterocyclic group; halogen; anitrogen-substituted group, such as amino, dialkyl amino, or nitro; or anitrogen-substituted ring compound, such as morpholino, piperidino, orpiperazino. Also in graphic formulas IIa and IIb, R₁, R₂, R₃, R₄, R₅,R₆, R₇, R₈, R₉, and R₁₀ are each selected from the following: a stableorganic radical, such as alkyl, alkoxy, unsubstituted or substitutedphenyl, unsubstituted or substituted phenoxy, naphthyl, nalphthoxy,cycloalkyl, furyl, alkoyl, alkoyloxy, aroyl, or aroyloxy; a heterocyclicgroup; halogen; a nitrogen-substituted group, such as amino,dialkylamino, or nitro; and a nitrogen-substituted ring compound, suchas morpholino, piperidino, or piperazino.

The benzopyran compounds represented by graphic formulas IIa and IIb arederivatives of 3,3-aryl-disubstituted-aryl chromenes. These benzopyrancompounds exhibit a surprising and highly desirable bathochromic shiftof the maximum activated wavelength. The bathochromic shift exhibited bythe inventive benzopyran compounds provide photochromic species whichturn orange, reddish-orange or purple when activated by a source ofultraviolet radiation. such as solar radiation or light radiated from amercury or xenon lamp.

It has been found desirable to produce photochromic compounds withmaximum activated wavelengths approaching and even exceeding 500nanometers. Photochromic compounds with maximum activated wavelengthsnear or above 500 nanometers change from original states of color todeep shades of orange, reddish-orange or red when activated byultraviolet light. The colored forms of the activated photochromiccompounds fade to the original, unactivated colored states at ambienttemperatures when isolated from the ultraviolet light. Photochromiccompounds that turn deep shades of orange, reddish orange, or red whenactivated are hereinafter referred to as "intense photochromes" forpurposes of this disclosure only.

The inventive benzopyrans represented by graphical formulas IIa and IIbespecially the intense photochromes, exhibit a deep color and a largerbathochromic shift in the visible spectrum of the activated form, ascompared to current naphthopyrans. Indeed, the inventive benzopyransrepresented by graphical formulas IIa and IIb, especially the intensephotochromes, approach, and in some cases exceed, a maximum activatedwavelength of 500 nanometers and exhibit deep shades of orange, reddishorange, or purple when activated. One of the inventive benzopyransrepresented by graphical formulas IIa and IIb surprisingly attains amaximum activated wavelength of 568 nanometers. Also, the inventivebenzopyrans represented by graphical formulas IIa and IIb haveacceptable fade characteristics.

One suitable method of preparing photochromic compounds having thestructure of graphic formulas IIa and IIb involves reacting a suitableketone precursor with a metal salt of an alkyne to make an intermediate.The intermediate is then reacted with either an unsubstituted fusedheterocycle or a substituted fused heterocycle in the presence of acatalyst. The resultant material is then purified by recrystallization,column chromatography, or a combination of recrystallization and columnchromatography.

One example of a suitable ketone precursor is 4-benzoylbiphenyl. Themetal salt of the alkyne is preferably lithium acetylide and the organicsolvent is preferably tetrahydrofuran. One example of the fusedheterocycle is 2-hydroxy-dibenzofuran. The catalyst is preferably acatalytic amount of p-toluenesulfonic acid.

Preferred benzopyran compounds, consistent with graphic formulas IIa andIIb, include the benzopyran compounds that may be represented by graphicformulas IIIa and IIIb below: ##STR5## The method set forth later inthis application for producing the photochromic benzopyran compounds ofgraphic formulas IIIa and IIIb forms a photochromic reaction productthat is believed to include both of the structural isomers that aredepicted in graphic formulas IIIa and IIIb.

When dissolved in chloroform, the photochromic reaction product thatincludes the photochromic benzopyran compound of graphical compounds ofgraphic formulas IIIa and IIIb unexpectedly exhibits two maximumactivated wavelengths of absorption at 456 nanometers and at 568nanometers when irradiated with ultraviolet light. Additionally, whenactivated by ultraviolet light, the photochromic reaction product thatincludes the photochromic benzopyran compounds of graphic formulas IIIaand IIIb turns a intense shade of gray. Therefore, when a gray-turningphotochromic compound is desired, the photochromic reaction product thatincludes the photochromic benzopyran compounds of graphic formulas IIIaand IIIb can be directly incorporated into the photochromic articlewithout first blending the photochromic reaction product with anotherphotochromic compound, such as a substituted spiroindolinonaphthoxazine.

The intense photochromes of the present invention may be blended withone or more other photochromic compounds of different maximum activationwavelengths from that of the inventive intense photochromes to makephoto-chromic mixtures. Preferably, the other photochromic compoundsturn colors other than orange, reddish orange and purple when activatedwith ultraviolet light. In one embodiment, one or more of the inventiveintense photochromes may be blended with another pholochromic compoundwhich has a different maximum activation wavelength and which turns bluewhen activated with ultraviolet light to make the photochromic mixture.Alternatively, the photochromic reaction product that includes thephotochromic benzopyran compounds of graphical formulas IIIa and IIIbmay be used alone to attain the gray color upon exposure to ultravioletlight. The photochromic mixtures and the photochromic reaction productmay be desirably applied to or incorporated within substrates, such asconventional synthetic plastic materials often used for opticalelements.

The benzopyran compounds represented by graphic formulas IIa and IIb maybe used in many applications of plastic substrates. For example,compounds represented by graphic formulas IIa and IIb may beincorporated into a host material that is applied to an article. Also,compounds represented by graphic formulas IIa and IIb may be combinedwith host material that is used to make the article. Additionally,compositions that contain one or more of the photochromic compoundsrepresented by graphic formulas IIa and IIb, such as the previouslymentioned photo-chromic mixtures or the photochromic reaction product,may be incorporated into the host material. The combination of thecomposition and host material, as already noted, may be applied to thearticle or may be used to make the article. Compounds represented bygraphic formulas IIa and IIb and compositions containing one or morecompounds represented by graphic formulas IIa and IIb may be coated ontothe host material, the article, or other suitable substrate.Furthermore, the photochromic reaction product that includes thephotochromic benzopyran compounds of graphic formulas IIIa and IIIb maybe coated onto the host material, the article, or other suitablesubstrate.

Polymerized organic materials, such as synthetic polymerized plasticoften used to make optical elements, are examples of the host material.Examples of the article include optical elements, such as piano andophthalmic lenses. Non-exhaustive illustrations of suitable syntheticpolymerized plastics suitable for use as the host material includepolyacrylate, polycarbonate, polyvinyl alcohol, polyvinyl acetate,polyvinyl chloride, polyurethane, cellulose ester and bis-polyol (allylcarbonate) monomer-based polymer.

As used in this disclosure, including the description and the claims,the term bis-polyol (allyl carbonate) monomer and similar phrases areintended to mean and include the named monomer or prepolymer and anyrelated monomer series contained therein. Some non-limiting examples ofbis-polyol (allyl carbonate) monomers include ethylene glycol bis(allylcarbonate), di-ethylene glycol bis(2-methylallyl carbonate), diethyleneglycol bis(allyl carbonate), propylene glycol bis(2-ethylallylcarbonate), 1-3-propanediol bis(allyl carbonate), 1,3-butanediolbis(allyl carbonate), 1,4-butanediol bis(2, bromoallyl carbonate),dipropylene glycol bis(allyl carbonate), trimethylene glycolbis(2-ethylallyl carbonate), pentamnethylene glycol bis(allylcarbonate), and isopropylidene bisphenol bis(allyl carbonate).

The amount of a particular one of the compounds represented by graphicformulas IIa or IIb, or a particular composition containing one of thecompounds represented by graphic formulas IIIa or IIIb, that isincorporated into the host material or the coating material is defined,for purposes of this disclosure, as the photochromic amount. Thephotochromic amount is not critical, provided that a sufficient amountto produce a photochromic effect perceptible to the human eye is used.The photochromic amount often depends on the desired intensity of thecolor on activation of the particular inventive benzopyran and on themethod of incorporation or application of the particular inventivebenzopyran. Typically, the photochromic amount incorporated into orapplied to the host material or incorporated into the coating materialranges from about 0.01 to about 20 percent by weight, based on theweight of the host material or the weight of the coating material, asapplicable.

The present invention is more particularly described in the followingexamples which are intended as illustrations only since numerousmodifications and variations within the scope of the general formulationwill be apparent to those skilled in the art.

EXAMPLE 1

Step 1

Five grams of 4-benzoylbiphenyl were placed together with five grams oflithium acetylide in 250 milliliters of tetrahydrofuran and stirred for72 hours. The resultant mixture was poured over ice and diluted withwater to form an organic layer and an aqueous layer. The organic layerwas separated from the aqueous layer and dried with anhydrous sodiumsulfate. The dried organic layer wag evaporated to obtain a solidmaterial. The solid material was then triturated with acetone. Thetriturated material was dissolved in a solvent and the solvent solutionwas cooled to yield a recrystallized compound. Nuclear magneticresonance (NMR) spectroscopy showed the resultant material to be arelatively pure propargyl alcohol.

Step2

Two grams of the propargyl alcohol obtained in Step 1 were mixed with1.25 grams of 2-hydroxydibenzofuran in 200 milliliters of benzene.Twenty milligrams of p-toluenesultonic acid were then added and themixture was stirred under reflux for 8 hours. The resultant mixture wascooled and washed with 10% aqueous sodium hydroxide. The organic solvent(benzene) was removed using a rotary evaporator. The resulting materialwas dissolved in hexane and the resulting hexane solution was cooled toyield a recrystallized product. The recrystallized product was shown bynuclear magnetic resonance (NMR) spectroscopy to contain the followingphotochromic compounds: ##STR6## Ultraviolet visible spectroscopyindicated that the recrystallized product of Step 2, when dissolved inchloroform and irradiated with ultraviolet light of 350 nanometerwavelength, had two maximum wavelengths of absorption at 456 nanometersand at 568 nanometers.

The two maximum absorption peaks at 456 nanometers and at 568 nanometersindicate that the recrystallized product of Step 2 consists of at leasttwo structural isomers of the photochromic compound, When therecrystallized product of Step 2 was dissolved in chloroform andsubjected to thin film chromatography, one elution peak was observed forthe recrystallized product. The presence of two structural isomers issupported by the thin film chromatography results, which indicate thatthe photochromic benzopyran compounds contained in the recrystallizedproduct all have the same molecular weight. Thus, it is believed thatthe recrystallized product obtained in Step 2 contains the followingphotochromic compounds: ##STR7##

COMPARATIVE EXAMPLE 1

Step 1

Five grams of 4-benzoylbiphenyl were placed together with 5 grams oflithium acetylide in 250 milliliters of tetrahydrofuran and stirred for72 hours. The resultant mixture was poured over ice and diluted withwater to form an organic layer and an aqueous layer. The organic layerwas separated from the aqueous layer and dried with anhydrous sodiumsulfate. The dried organic material was evaporated to obtain a solidmaterial. The solid material was triturated with acetone. Nuclearmagnetic resonance (NMR) spectroscopy showed the resultant material tobe relatively pure diphenyl propargyl alcohol.

Step 2

Two grams of the diphenyl propargyl alcohol obtained in Step 2 weremixed with 1.71 grams of 6-methoxy-2-naphthol in 200 milliliters ofbenzene. Twenty milligrams of p-toluenesulfonic acid were then added andthe mixture was stirred under reflux for 8 hours. The resultant mixturewas cooled and washed with 10% aqueous sodium hydroxide. The organicsolvent (benzene) was removed using a rotary evaporator. The resultingmaterial was dissolved in hexane and the resultant hexane solution wascooled to yield a recrystallized product. The recrystallized product wasshown to be relatively pure3-(4-biphenylyl)-3-phenyl-8-methoxy-3H-naphtho 2,1b!pyran by nuclearmagnetic resonance NMR spectroscopy.

The recrystallized product formed in Step 2 of Example 1; the3-(4-biphenytyl)-3-phenyl-8-methoxy-3H-naphtho 2,1b!pyran formed inComparative Example 1; and a purchased sample of3,3-diphenyl-3H-naphtho- 2,1b!pyran (identified as Comparative Example2) were each individually dissolved in chloroform in separatecontainers. These chloroform dissolved substances were then irradiatedwith ultraviolet light with a maximum wavelength of 350 manometers andmeasured for maximum absorption wavelength, λ_(max). The fade time,T_(1/2), was then determined for each of the irradiated substances. Thefade time for of the chloroform-dissolved substances is defined as thetime interval, at room temperature (72° F.), for the absorbance of theactivated form of each chloroform-dissolved substance to decrease to onehalf of the maximum absorbance, after the substance is isolated from theactivating source of ultraviolet light. The maximum absorptionwavelength and fade time determined for the irradiated substances ofExample 1 and Comparative Examples 1-2 are presented in Table 1:

                  TABLE 1    ______________________________________                    λ.sub.max                            T.sub.1/2                     nanometers!                             seconds!    ______________________________________    SOLVENT           Chloroform                                Chloroform    EXAMPLE 1         456, 568  10.2    COMPARATIVE EXAMPLE    1                 484       **    2                 434       13    ______________________________________     Comparative Example 2: Purhased 3,3diphenyl-3H-naphtho- 2,1b!pyran     **Not Determined

The values presented in Table 1 illustrate that the inventivephotochromic product of Example 1 has one maximum wavelength ofactivation that is longer than that of the3-(4-biphenylyl)-3-phenyl-8-methoxy-3H-naphtho 2,1b!pyran of ComparativeExample 1 and the 3,3-diphenyl-3H-naphtho- 2,1b!pyran of ComparativeExample 2 and also has one maximum wavelength of activation that isshorter than that of the 3-(4-biphenylyl)-3-phenyl- 8-methoxy-3H-naphtho2,1b!pyran of Comparative Example 1. This combination of both longer andshorter maximum wavelengths of activation for the inventive photochromicproduct is a desirable characteristic for photochromic compositions.Additionally, the fade time, T_(1/2), of the inventive photochromicproduct of Example 1 is 10.2 seconds, which is a desirable fade time forphotochromic compositions.

Although the present invention has been described with reference topreferred embodiments, workers skilled in the art will recognize thatchanges may be made in form and detail without departing from the spiritand scope of the invention.

What is claimed is:
 1. A benzopyran compound represented by the formula:##STR8##
 2. A benzopyran product, the benzopyran product comprising:abenzopyran compound represented by the formula: ##STR9## anotherbenzopyran compound represented by the formula: ##STR10##
 3. Abenzopyran compound represented by the formula: ##STR11## wherein R₁,R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₆ ', R₇ ', R₈ ', and R₉ ' are eachselected from the group consisting of hydrogen, alkyl, alkoxy,substituted phenyl, unsubstituted phenyl, substituted phenoxy,unsubstituted phenoxy, naphthyl, naphthoxy, cycloalkyl, furyl, alkoyl,alkoyloxy, aroyl, aroyloxy, halogen, amino, dialkyl amino, nitro,morpholino, piperidino, and piperazino, provided that:at least one ofR₂, R₃, R₄, R₅, R₆, R₇, R₈, and R₉ is selected from the group consistingof substituted phenyl, unsubstituted phenyl, substituted phenoxy,unsubstituted phenoxy, naphthyl, naphthoxy, furyl, alkoyl, alkoyloxy,aroyl, aroyloxy, amino, nitro, morpholino, piperidino, and piperazino.4. The benzopyran compound according to claim 3 wherein R₆ ', R₇ ', R₈', and R₉ ' are each selected from the group consisting of hydrogen, C₁-C₂ alkyl, methoxy and ethoxy.
 5. The benzopyran compound according toclaim 3 wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₆ ', R₇ ', R₈', and R₉ ' are each selected from the group consisting of hydrogen,alkyl, alkoxy, substituted phenyl, unsubstituted phenyl, substitutedphenoxy, unsubstituted phenoxy, naphthyl, naphthoxy, cycloalkyl, furyl,alkoyl, alkoyloxy, aroyl, aroyloxy, halogen, amino, dialkyl amino,nitro, morpholino, piperidino, and piperazino, provided that:at leastone of R₂, R₃, R₄, R₅, R₆, R₇, R₈, and R₉ is selected from the groupconsisting of substituted phenyl, unsubstituted phenyl, substitutedphenoxy, unsubstituted phenoxy, furyl, alkoyl, alkoyloxy, aroyl,aroyloxy, amino, nitro, morpholino, piperidino, and piperazino.
 6. Thebenzopyran compound according to claim 3 wherein R₁, R₂, R₃, R₄, R₅, R₆,R₇, R₈, R₉, R₁₀, R₆ ', R₇ ', R₈ ', and R₉ ' are each selected from thegroup consisting of hydrogen, alkyl, alkoxy, substituted phenyl,unsubstituted phenyl, substituted phenoxy, unsubstituted phenoxy,naphthyl, naphthoxy, cycloalkyl, furyl, alkoyl, alkoyloxy, aroyl,aroyloxy, halogen, amino, dialkyl amino, nitro, morpholino, piperidino,and piperazino, provided that:at least one of R₂, R₃, R₄, R₅, R₆, R₇,R₈, and R₉ is selected from the group consisting of substituted phenyl,unsubstituted phenyl, substituted phenoxy, unsubstituted phenoxy, furyl,alkoyl, alkoyloxy, aroyl, aroyloxy, morpholino, piperidino, andpiperazino.
 7. The benzopyran compound according to claim 3 wherein R₁,R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₆ ',R₇ ', R₈ ', and R₉ ' are eachselected from the group consisting of hydrogen, alkyl, alkoxy,substituted phenyl, unsubstituted phenyl, substituted phenoxy,unsubstituted phenoxy, naphthyl, naphthoxy, cycloalkyl, furyl, alkoyl,alkoyloxy, aroyl, aroyloxy, halogen, amino, dialkyl amino, nitro,morpholino, piperidino, and piperazino, provided that:at least one ofR₂, R₃, R₄, R₅, R₆, R₇, R₈, and R₉ is selected from the group consistingof substituted phenyl, unsubstituted phenyl, substituted phenoxy,unsubstituted phenoxy, morpholino, piperidino, and piperazino.
 8. Thebenzopyran compound according to claim 3 wherein R₁, R₂, R₃, R₄, R₅, R₆,R₇, R₈, R₉, R₁₀, R₆ ', R₇ ', R₈ ', and R₉ ' are each selected from thegroup consisting of hydrogen, alkyl, alkoxy, substituted phenyl,unsubstituted phenyl, substituted phenoxy, unsubstituted phenoxy,naphthyl, naphthoxy, cycloalkyl, furyl, alkoyl, alkoyloxy, aroyl,aroyloxy, halogen, amino, dialkyl amino, nitro, morpholino, piperidino,and piperazino, provided that:at least one of R₂, R₃, R₄, R₅, R₆, R₇,R₈, and R₉ is selected from the group consisting of substituted phenyl,substituted phenoxy, furyl, alkoyl, alkoyloxy, aroyl, aroyloxy, amino,nitro, morpholino, piperidino, and piperazino.
 9. The benzopyrancompound according to claim 3 wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈,R₉, R₁₀, R₆ ', R₇ ', R₈ ', and R₉ ' are each selected from the groupconsisting of hydrogen, alkyl, alkoxy, substituted phenyl, unsubstitutedphenyl, substituted phenoxy, unsubstituted phenoxy, naphthyl, naphthoxy,cycloalkyl, furyl, alkoyl, alkoyloxy, aroyl, aroyloxy, halogen, amino,dialkyl amino, nitro, morpholino, piperidino, and piperazino, providedthat:at least one of R₂, R₃, R₄, R₅, R₆, R₇, R₈, and R₉ is selected fromthe group consisting of unsubstituted phenyl, unsubstituted phenoxy,furyl, alkoyl, alkoyloxy, aroyl, aroyloxy, amino, nitro, morpholino,piperidino, and piperazino.
 10. The benzopyran compound according toclaim 3 wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₆ ', R₇ ', R₈', and R₉ ' are each selected from the group consisting of hydrogen,alkyl, alkoxy, substituted phenyl, unsubstituted phenyl, substitutedphenoxy, unsubstituted phenoxy, naphthyl, naphthoxy, cycloalkyl, furyl,alkoyl, alkoyloxy, aroyl, aroyloxy, halogen, amino, dialkyl amino,nitro, morpholino, piperidino, and piperazino, provided that:at leastone of R₂, R₃, R₄, R₅, R₆, R₇, R₈, and R₉ is selected from the groupconsisting of substituted phenyl, unsubstituted phenyl, substitutedphenoxy, unsubstituted phenoxy, furyl, alkoyl, alkoyloxy, aroyl,aroyloxy, amino, and nitro.
 11. The benzopyran compound according toclaim 3 wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₆ ', R₇ ', R₈', and R₉ ' are each selected from the group consisting of hydrogen,alkyl, alkoxy, substituted phenyl, unsubstituted phenyl, substitutedphenoxy, unsubstituted phenoxy, naphthyl, naphthoxy, cycloalkyl, furyl,alkoyl, alkoyloxy, aroyl, aroyloxy, halogen, amino, dialkyl amino,nitro, morpholino, piperidino, and piperazino, provided that:at leastone of R₂, R₃, R₄, R₅, R₆, R₇, R₈, and R₉ is selected from the groupconsisting of morpholino, piperidino, and piperazino.
 12. A benzopyranproduct, the benzopyran product comprising:a benzopyran compoundrepresented by the formula: ##STR12## another benzopyran compoundrepresented by the formula: ##STR13## wherein R₁, R₂, R₃, R₄, R₅, R₆,R₇, R₈, R₉, R₁₀, R₆ ', and R₇ ', R₈ ', R₉ ' are each selected from thegroup consisting of hydrogen, alkyl, alkoxy, substituted phenyl,unsubstituted phenyl, substituted phenoxy, unsubstituted phenoxy,naphthyl, naphthoxy, cycloalkyl, furyl, alkoyl, alkoyloxy, aroyl,aroyloxy, halogen, amino, dialkyl amino, nitro, morpholino, piperidino,and piperazino, provided that: at least one of R₂, R₃, R₄, R₅, R₆, R₇,R₈, and R₉ is selected from the group consisting of substituted phenyl,unsubstituted phenyl, substituted phenoxy, unsubstituted phenoxy,naphthyl, naphthoxy, furyl, alkoyl, alkoyloxy, aroyl, aroyloxy, amino,nitro, morpholino, piperidino, and piperazino.
 13. A benzopyran compoundrepresented by the formula: ##STR14## wherein R₁, R₂, R₃, R₄, R₅, R₆,R₇, R₈, R₉, R₁₀, R₆ ', R₇ ', R₈ ', and R₉ ' are each selected from thegroup consisting of hydrogen, alkyl, alkoxy, substituted phenyl,unsubstituted phenyl, substituted phenoxy, unsubstituted phenoxy,naphthyl, naphthoxy, cycloalkyl, furyl, alkoyl, alkoyloxy, aroyl,aroyloxy, halogen, amino, nitro, morpholino, piperidino, and piperazino,provided that:at least one of R₂, R₃, R₄, R₅, R₆, R₇, R₈, and R₉ isselected from the group consisting of substituted phenyl, unsubstitutedphenyl, substituted phenoxy, unsubstituted phenoxy, naphthyl, naphthoxy,furyl, alkoyl, alkoyloxy, aroyl, aroyloxy, amino, nitro, morpholino,piperidino, and piperazino.
 14. The benzopyran compound according toclaim 13 wherein R₆ ', R₇ ', R₈ ', and R₉ ' are each selected from thegroup consisting of hydrogen, C₁ -C₂ alkyl, methoxy and ethoxy.
 15. Thebenzopyran compound according to claim 13 wherein R₁, R₂, R₃, R₄, R₅,R₆, R₇, R₈, R₉, R₁₀, R₆ ', R₇ ', R₈ ', and R₉ ' are each selected fromthe group consisting of hydrogen, alkyl, alkoxy, substituted phenyl,unsubstituted phenyl, substituted phenoxy, unsubstituted phenoxy,naphthyl, naphthoxy, cycloalkyl, furyl, alkoyl, alkoyloxy, aroyl,aroyloxy, halogen, amino, dialkyl amino, nitro, morpholino, piperidino,and piperazino, provided that:at least one of R₂, R₃, R₄, R₅, R₆, R₇,R₈, and R₉ is selected from the group consisting of substituted phenyl,unsubstituted phenyl, substituted phenoxy, unsubstituted phenoxy, furyl,alkoyl, alkoyloxy, aroyl, aroyloxy, amino, nitro, morpholino,piperidino, and piperazino.
 16. The benzopyran compound according toclaim 13 wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₆ ', R₇ ', R₈', and R₉ ' are each selected from the group consisting of hydrogen,alkyl, alkoxy, substituted phenyl, unsubstituted phenyl, substitutedphenoxy, unsubstituted phenoxy, naphthyl, naphthoxy, cycloalkyl, furyl,alkoyl, alkoyloxy, aroyl, aroyloxy, halogen, amino, dialkyl amino,nitro, morpholino, piperidino, and piperazino, provided that:at leastone of R₂, R₃, R₄, R₅, R₆, R₇, R₈, and R₉ is selected from the groupconsisting of substituted phenyl, unsubstituted phenyl, substitutedphenoxy, unsubstituted phenoxy, furyl, alkoyl, alkoyloxy, aroyl,aroyloxy, morpholino, piperidino, and piperazino.
 17. The benzopyrancompound according to claim 13 wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇,R₈,R₉, R₁₀, R₆ ', R₇ ', R₈ ', and R₉ ' are each selected from the groupconsisting of hydrogen, alkyl, alkoxy, substituted phenyl, unsubstitutedphenyl, substituted phenoxy, unsubstituted phenoxy, naphthyl, naphthoxy,cycloalkyl, furyl, alkoyl, alkoyloxy, aroyl, aroyloxy, halogen, amino,dialkyl amino, nitro, morpholino, piperidino, and piperazino, providedthat:at least one of R₂, R₃, R₄, R₅, R₆, R₇, R₈, and R₉ is selected fromthe group consisting of substituted phenyl, unsubstituted phenyl,substituted phenoxy, unsubstituted phenoxy, morpholino, piperidino, andpiperazino.
 18. The benzopyran compound according to claim 13 whereinR₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R ₁₀, R₆ ', R₇ ', R₈ ', and R₉ ' areeach selected from the group consisting of hydrogen, a alkoxy,substituted phenyl, unsubstituted phenyl, substituted phenoxy,unsubstituted phenoxy, naphthyl, naphthoxy, cycloalkyl, furyl, alkoyl,alkoyloxy, aroyl, aroyloxy, halogen, amino, dialkyl amino, nitro,morpholino, piperidino, and piperazino, provided that:at least one ofR₂, R₃, R₄, R₅, R₆, R₇, R₈, and R₉ is selected from the group consistingof substituted phenyl, substituted phenoxy, furyl, alkoyl, alkoyloxy,aroyl, aroyloxy, amino, nitro, morpholino, piperidino, and piperazino.19. The benzopyran compound according to claim 13 wherein R₁, R₂, R₃,R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₆ ', R₇ ', R₈ ', and R₉ ' are eachselected from the group consisting of hydrogen, alkyl, alkoxy,substituted phenyl, unsubstituted phenyl, substituted phenoxy,unsubstituted phenoxy, naphthyl, naphthoxy, cycloalkyl, furyl, alkoyl,alkoyloxy, aroyl, aroyloxy, halogen, amino, dialkyl amino, nitro,morpholino, piperidino, and piperazino, provided that:at least one ofR₂, R₃, R₄, R₅, R₆, R₇, R₈, and R₉ is selected from the group consistingof unsubstituted phenyl, unsubstituted phenoxy, furyl, alkoyl,alkoyloxy, aroyl, aroyloxy, amino, nitro, morpholino, piperidino, andpiperazino.
 20. The benzopyran compound according to claim 13 whereinR₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₆ ', R₇ ', R₈ ', and R₉ ' areeach selected from the group consisting of hydrogen, alky alkoxy,substituted phenyl, unsubstituted phenyl, substituted phenoxy,unsubstituted phenoxy, naphthyl, naphthoxy, cycloalkyl, furyl, alkoyl,alkoyloxy, aroyl, aroyloxy, halogen, amino, dialkyl amino, nitro,morpholino, piperidino, and piperazino, provided that:at least one ofR₂, R₃, R₄, R₅, R₆, R₇, R₈, and R₉ is selected from the group consistingof substituted phenyl, unsubstituted phenyl, substituted phenoxy,unsubstituted phenoxy, furyl, alkoyl, alkoyloxy, aroyl, aroyloxy, amino,and nitro.
 21. The benzopyran compound according to claim 13 wherein R₁,R₂, R₃, R₄, R_(b) 5, R₆, R₇, R₈, R₉, R₁₀, R₆ ', R₇ ', R₈ ', and R₉ ' areeach selected from the group consisting of hydrogen, alkyl, alkoxy,substituted phenyl, unsubstituted phenyl, substituted phenoxy,unsubstituted phenoxy, naphthyl, naphthoxy, cycloalkyl, furyl, alkoyl,alkoyloxy, aroyl, aroyloxy, halogen, amino, dialkyl amino, nitro,morpholino, piperidino, and piperazino, provided that:at least one ofR₂, R₃, R₄, R₅, R₆, R₇, R₈, and R₉ is selected from the group consistingof morpholino, piperidino, and piperazino.
 22. The benzopyran compoundaccording to claim 13 wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀,R₆ ', R₇ ', R₈ ', and R₉ ' are each selected from the group consistingof hydrogen, alkyl, alkoxy, substituted phenyl, unsubstituted phenyl,substituted phenoxy, unsubstituted phenoxy, naphthyl, naphthoxy,cycloalkyl, furyl, alkoyl, alkoyloxy, aroyl, aroyloxy, halogen, amino,dialkyl amino, nitro, morpholino, piperidino, and piperazino, providedthat:at least one of R₂, R₃, R₄, R₅, R₆, R₇, R₈, and R₉ is selected fromthe group consisting of substituted phenyl, unsubstituted phenyl,substituted phenoxy, and unsubstituted phenoxy.
 23. A benzopyrancompound represented by the formula: ##STR15##